Fluorination of Perhalogen Olefins

Abstract

CHEMISTRY 401 and 80 grams (0.27 mole) of antimony pentachloride were placed in the autoclave: the mixture was heated at 340°C. for 48 hours with constant agitation. The autoclave was then cooled to room temperature, and liquid products were decanted from solid antimony salts remaining in the reaction vessel. The fluorinated material was washed with dilute hydrochloric acid and steamdistilled. Two hundred grams of crude product were obtained, dried, and rectified. Three separate fractions were obtained and identified as 45 grams of l-(heptafluoroisopropyl)-4-(trifluoromethyl)benzene, 83 grams of l-(chlorohexafluoroisopropyl)-4-(trifiuoromethyl)benzene, and 35 grams of l-(dichloropentafluoroisopropyl)-4-(trifiuoromethyl)benzene. Conversion to 1-(heptafluoroisopropvl)-4-(trifluoromethyl)benzene was 15% and the yield 50%. 2. Five hundred seventy-four grams of a mixture composed of 279 grams (1.0 mole) of (dichloropentafluoroisopropyl)benzene, 295 grams (1.0 mole) of (trichlorotetrafluoroisopropyl) benzene, 400 grams (2.2 moles) of powdered antimony trifluoride, and 90 grams (0.3 mole) of antimony pentachloride were placed in the autoclave. The reaction was heated at 330°C. for 30 hours and then cooled to room temperature, and the liquid products were decanted. The fluorinated product was treated as described, 219 grams of product being obtained. Rectification yielded three fractions: 49 grams of (heptafluoroisopropyl)benzene, 79 grams of (chiorohcxafluoroisopropyl)benzene, and 56 grams of (dichloropentafluoroisopropyl)benzene. Conversion to (heptafluoroisopropyl)benzene was 10%, and to (chlorohexafluoroisopropyl)benzene 15%. The yield was 35%.The compounds were purified by rectification in a Podbivlniak Hyper-Cal column. The physical constants arid halogen analyses are given in Table I.

Fluorine Compounds, Organic

“…Stabilization and end-group fluorination are achieved using cobalt trifluoride as fluorinating agent [98,99].…”

Plastics

“…Polychlorotrifluoroethylene may prove to have the advantages of the chemical inertness of the completely fluorinated ethylene polymer combined with easier formability (60).…”

Aerosol direct fluorination of C1 and C2 chlorocarbons

“…In a paper concerning the solution-phase fluorination of chlorocarbons, Miller (1940) observed the formation of CFC13 from chloroform as well as from the addition of F2 to tetrachloroethylene. Miller's work with chlorooleflns (Miller and Dittman, 1956; Miller and Koch, 1957;Miller et al, 1947 Miller et al, ,1967 has become a classic study of these substrates.…”